Resin material for gas separation base and process for producing the same

Abstract

This invention relates to resin material for gas separation base containing a cardo polyimide structure in which the hydrogen atoms in the side-chain benzyl and/or allyl position are halogenated at a rate of modification by halogen of 0.1% or more or resin material for gas separation base containing polymer in which the hydrogen atoms in the side-chain benzyl and/or allyl position are halogenated at a rate of modification by halogen of 34% or more and, additionally, relates to polymer which serves as raw material for the aforementioned resin material for gas separation base containing a cardo polymer structure and a process for producing said polymer; said polymer not only excels in such properties as solvent solubility, ease of conversion to film by a wet process, thermal stability, and chemical stability but also performs well in gas permeability and the process of this invention makes it possible to produce gas separation base, particularly gas separation membrane, whose gas permeability and gas selectivity can be readily controlled.

What is claimed is:  
     
       1. A gas separation material, comprising: 
       a resin material for gas separation base comprising polymer of a cardo structure in which hydrogen atoms in a side-chain benzyl and/or allyl position are halogenated at a rate of modification by halogen of 0.1% or more.  
     
     
       2. Resin material for gas separation base as described in  claim 1 , wherein said polymer is polyimide. 
     
     
       3. Resin material for gas separation base as described in  claim 1 , wherein said polymer is polyimide of a cardo structure represented by the following general formula (1)                    
       wherein X is a divalent residue of an organic group and at least partly a divalent residue of an organic group represented by the following structural formula (A)                    
       and Y is a tetravalent residue of an organic group; in the structural formula (A), at least one of R 1  to R 20  is a halogen-modified substituent represented by 
       
         
           —CZR 21 R 22    
         
       
       (wherein Z is a halogen atom and R 21  and R 22  will be defined later), the remainder of R 1  to R 20  and R 21  and R 22  in the halogen-modified substituent are hydrogen, halogen, linear or branched or cyclic unsubstituted or substituted alkyl, alkenyl, alkynyl, or aryl group; the aforementioned alkyl, alkenyl, alkynyl, and aryl groups may contain one kind or two kinds or more of hetero atoms selected from nitrogen, oxygen, sulfur, phosphorus and halogens and may be identical with or different from one another, the aforementioned remainder of R 1  to R 20  and R 21  and R 22  may pair and join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure, any one of R 11  to R 15  and any one of R 16  to R 20  are respectively bonded to the nitrogen atom in the imide skeleton, and any one of R 1  to R 5  and any one of R 6  to R 10  join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure. 
     
     
       4. Resin material for gas separation base as described in  claim 3 , wherein the structural formula (A) in the general formula (1) is a divalent residue of an organic group containing a fluorene skeleton represented by the following structural formula (B)                    
       wherein R 1  to R 4  and R 7  to R 20  are as defined in the case of the structural formula (A). 
     
     
       5. Resin material for gas separation base as described in  claim 4 , wherein at least one substituent selected from R 11  to R 20  is a halogen-modified substituent. 
     
     
       6. Resin material for gas separation base as described in any one of  claims 1  to  5 , wherein the rate of modification by halogen of the hydrogen atoms in the side-chain benzyl and/or allyl position is 20% or more. 
     
     
       7. Resin material for gas separation base comprising polyimide of a cardo-type structure represented by the following general formula (1)                    
       wherein X is a divalent residue of an organic group and at least partly a divalent residue of an organic group represented by the following structural formula (A)                    
       and Y is a tetravalent residue of an organic group; in the structural formula (A), at least one of R 1  to R 20  is a functional group-modified substituent represented by 
       
         
           —CFuZR 21 R 22 , —CFu 2 R 21  and/or —CFu 3    
         
       
       (wherein Fu is a functional group or a derivative thereof which can be introduced by replacing a halogen atom in the benzyl and/or allyl position), the remainder of R 1  to R 20  and R 21  and R 22  are hydrogen, halogen, linear or branched or cyclic unsubstituted or substituted alkyl, alkenyl, alkynyl, or aryl group; the aforementioned alkyl, alkenyl, alkynyl, and aryl groups may contain one kind or two kinds or more of hetero atoms selected from nitrogen, oxygen, sulfur, phosphorus and halogens and may be identical with or different from one another, the aforementioned remainder of R 1  to R 20  and R 21  and R 22  may pair and join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure, any one of R 11  to R 15  and any one of R 16  to R 20  are respectively bonded to the nitrogen atom in the imide skeleton, and any one of R 1  to R 5  and any one of R 6  to R 10  join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure. 
     
     
       8. Resin material for gas separation base as described in  claim 7 , wherein the structural formula (A) in the general formula (1) is a divalent residue of an organic group containing a fluorene skeleton represented by the following structural formula (B)                    
       wherein R 1  to R 4  and R 7  to R 20  are as defined in the case of the structural formula (A). 
     
     
       9. Resin material for gas separation base as described in  claim 8 , wherein at least one substituent selected from R 11  to R 20  is a functional group-modified substituent. 
     
     
       10. Resin material for gas separation base comprising polymer in which the hydrogen atoms in the side-chain benzyl and/or allyl position are halogenated at a rate of modification by halogen of 34% or more. 
     
     
       11. Resin material for gas separation base as described in  claim 10 , wherein said polymer is polyimide. 
     
     
       12. Polymer containing a structure of cardo polyimide represented by the following general formula (1)                    
       wherein X is a divalent residue of an organic group and at least partly a divalent residue of an organic group represented by the following structural formula (A)                    
       and Y is a tetravalent residue of an organic group; in the structural formula (A), at least one of R 1  to R 20  is a halogen-modified substituent represented by 
       
         
           —CZR 21 R 22    
         
       
       (wherein Z is a halogen atom and R 21  and R 22  will be defined later), the remainder of R 1  to R 20  and R 21  and R 22  in the halogen-modified substituent are hydrogen, halogen, linear or branched or cyclic unsubstituted or substituted alkyl, alkenyl, alkynyl, or aryl group; the aforementioned alkyl, alkenyl, alkynyl, and aryl groups may contain one kind or two kinds or more of hetero atoms selected from nitrogen, oxygen, sulfur, phosphorus and halogens and may be identical with or different from one another, the aforementioned remainder of R 1  to R 20  and R 21  and R 22  may pair and join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure, any one of R 11  to R 15  and any one of R 16  to R 20  are respectively bonded to the nitrogen atom in the imide skeleton, and any one of R 1  to R 5  and any one of R 6  to R 10  join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure. 
     
     
       13. Polymer as described in  claim 12 , wherein the structural formula (A) in the general formula (1) is a divalent residue of an organic group containing a fluorene skeleton represented by the following structural formula (B)                    
       wherein R 1  to R 4  and R 7  to R 20  are as defined earlier. 
     
     
       14. Polymer as described in  claim 13 , wherein at least one substituent selected from R 11  to R 20  is a halogen-modified substituent. 
     
     
       15. Polymer as described in any one of  claims 12  to  14 , wherein the rate of modification by halogen in the side-chain benzyl and/or allyl position is 20% or more. 
     
     
       16. Polymer containing a structure of cardo polyimide represented by the following general formula (1)                    
       wherein X is a divalent residue of an organic group and at least partly a divalent residue of an organic group represented by the following structural formula (A)                    
       and Y is a tetravalent residue of an organic group; in the structural formula (A), at least one of R 1  to R 20  is a functional group-modified substituent represented by 
       
         
           —CFuZR 21 R 22 , —CFu 2 R 21  and/or —CFu 3    
         
       
       (wherein Fu is a functional group or a derivative thereof which can be introduced by replacing a halogen atom in the benzyl and/or allyl position), the remainder of R 1  to R 20  and R 21  and R 22  are hydrogen, halogen, linear or branched or cyclic unsubstituted or substituted alkyl, alkenyl, alkynyl, or aryl group; the aforementioned alkyl, alkenyl, alkynyl, and aryl groups may contain one kind or two kinds or more of hetero atoms selected from nitrogen, oxygen, sulfur, phosphorus and halogens and may be identical with or different from one another, the aforementioned remainder of R 1  to R 20  and R 21  and R 22  may pair and join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure, any one of R 11  to R 15  and any one of R 16  to R 20  are respectively bonded to the nitrogen atom in the imide skeleton; and any one of R 1  to R 5  and any one of R 6  to R 10  join together to form a saturated or unsaturated bond in a cyclic structure. 
     
     
       17. Polymer as described in  claim 16 , wherein the structural formula (A) in the general formula (1) is a divalent residue of an organic group containing a fluorene skeleton represented by the following structural formula (B)                    
       wherein R 1  to R 4  and R 7  to R 20  are as defined earlier. 
     
     
       18. Polymer as described in  claim 17 , wherein at least one substituent selected from R 11  to R 20  is a functional group-modified substituent. 
     
     
       19. A process for producing polymer containing a structure of halogen-modified cardo polyimide from a polymer containing a structure of cardo polyimide represented by the following general formula (1)                    
       wherein X is a divalent residue of an organic group and at least partly a divalent residue of an organic group represented by the following structural formula (A)                    
       and Y is a tetravalent residue of an organic group; in the structural formula (A), at least one of R 1  to R 20  is a pre-modification substituent represented by 
       
         
           —CHR 21 R 22    
         
       
       (wherein R 21  and R 22  are as defined later), the remainder of R 1  to R 20  and R 21  and R 22  are hydrogen, halogen, linear or branched or cyclic unsubstituted or substituted alkyl, alkenyl, alkynyl, or aryl group; the aforementioned alkyl, alkenyl, alkynyl, and aryl groups may contain one kind or two kinds or more of hetero atoms selected from nitrogen, oxygen, sulfur, phosphorus and halogens and may be identical with or different from one another, the aforementioned remainder of R 1  to R 20  and R 21  and R 22  may pair and join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure, any one of R 11  to R 15  and any one of R 16  to R 20  are respectively bonded to the nitrogen atom in the imide skeleton, and any one of R 1  to R 5  and any one of R 6  to R 10  join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure; said process comprises treating said polymer containing a structure of cardo polyimide with a halogenating agent in mole equivalent corresponding to 0.01 to 3 times that of the hydrogen atoms in the benzyl and/or allyl position in said pre-modification substituent and effecting the reaction at a rate of modification by halogen of 0.1% or more to give said polymer containing a structure of halogen-modified cardo polyimide whose halogen-modified substituent is represented by 
       
         
           —CZR 21 R 22    
         
       
       (wherein Z is a halogen atom and R 21  and R 22  are as defined earlier). 
     
     
       20. A process for producing polymer as described in  claim 19 , wherein the structural formula (A) in the general formula (1) contains a fluorene skeleton represented by the following structural formula (B)                    
       wherein R 1  to R 4  and R 7  to R 20  are as defined earlier. 
     
     
       21. A process for producing polymer as described in  claim 20 , wherein at least one substituent selected from R 11  to R 20  is a halogen-modified substituent. 
     
     
       22. A process for producing polymer as described in any one of  claims 19  to  21 , wherein the rate of modification by halogen of the hydrogen atoms in the side-chain benzyl and/or allyl position is 20% or more. 
     
     
       23. A process for producing polymer containing a functional group-modified substituent from a polymer containing a structure of cardo polyimide represented by the following general formula (1)                    
       wherein X is a divalent residue of an organic group and at least partly a divalent residue of an organic group represented by the following structural formula (A)                    
       and Y is a tetravalent residue of an organic group; in the structural formula (A), at least one of R 1  to R 20  is a pre-modification substituent represented by 
       
         
           —CHR 21 R 22    
         
       
       (wherein R 21  and R 22  are as defined later), the remainder of R 1  to R 20  and R 21  and R 22  in the pre-modification substituent are hydrogen, halogen, linear or branched or cyclic unsubstituted or substituted alkyl, alkenyl, alkynyl, or aryl group; the aforementioned alkyl, alkenyl, alkynyl, and aryl groups may contain one kind or two kinds or more of hetero atoms selected from nitrogen, oxygen, sulfur, phosphorus and halogens and may be identical with or different from one another, the aforementioned remainder of R 1  to R 20  and R 21  and R 22  may pair and join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure, any one of R 11  to R 15  and any one of R 16  to R 20  are respectively bonded to the nitrogen atom in the imide skeleton, and any one of R 1  to R 5  and any one of R 6  to R 10  join together directly or through another atom to form a saturated or unsaturated bond in a cyclic structure; said process comprises treating said polymer containing a structure of cardo polyimide with a halogenating agent in mole equivalent corresponding to 0.01 to 3 times that of the hydrogen atoms in the benzyl and/or allyl position in said pre-modification substituent, effecting the reaction at a rate of modification by halogen of 0.1% or more to give polymer containing a structure of halogen-modified cardo polyimide whose halogen-modified substituent is represented by 
       
         
           —CZR 21 R 22    
         
       
       (wherein Z is a halogen atom and R 21  and R 22  are as defined earlier), and treating the resulting polymer with a nucleophilic reagent containing a functional group capable of undergoing substitution with the halogen atom in the halogen-modified substituent thereby converting at least a part of said halogen-modified substituent to a functional group-modified substituent represented by 
       
         
           —CFuR 21 R 22 , —CFu 2 R 21  and/or —CFu 3    
         
       
       (wherein Fu is a functional group or a derivative thereof which can be introduced by replacing a halogen atom in the benzyl and/or allyl position). 
     
     
       24. Resin material for gas separation membrane as described in  claim 1  in the form of gas separation membrane. 
     
     
       25. Cardo polymer in which hydrogen atoms in a side-chain benzyl and/or allyl position are halogenated at a rate of modification by halogen of 0.1% or more. 
     
     
       26. Cardo polymer as described in  claim 25 , wherein said polymer is polyimide. 
     
     
       27. Polymer containing cardo polymer modified by functional groups at least one of which is represented by 
       
         
           —CFuR 21 R 22 , —CFu 2 R 21  and/or —CFu 3    
         
       
       wherein Fu is a functional group or a derivative thereof which can be introduced by replacing a halogen atom in a side chain benzyl and/or allyl position and R 21  and R 22  are hydrogen, halogen, linear or branched or cyclic unsubstituted or substituted alkyl, alkenyl, alkynyl or aryl group, may contain one kind or two kinds or more of hetero atoms selected from nitrogen, oxygen, sulfur, phosphorus and halogens, may be identical with or different from one another, and may join together or to other carbon atoms to form a saturated or unsaturated bond in cyclic structure. 
     
     
       28. Polymer as described in  claim 27 , wherein said polymer is polyimide. 
     
     
       29. Polymer as described in  claim 27  useful for resin material for gas separation base. 
     
     
       30. Polymer as described in  claim 28  useful for resin material for gas separation base. 
     
     
       31. Resin material for gas separation base as described in  claim 29  or  30  in the form of gas separation membrane.